Tuning the micro-phase separation of the PES-g-PEG comb-like copolymer membrane for efficient CO2 separation

As a common CO2 separation membrane material, polyethylene glycol (PEG) with ether oxygen groups shows high dissolution selectivity to CO2. However, high molecular weight PEG has strong crystallinity, resulting in low gas flux, while the low molecular weight PEG has poor mechanical properties. Block copolymers containing PEG segments can address this challenge but are difficult to synthesize. In this work, a series of polyether sulfone (PES) comb-like copolymer with PEG side chains were prepared by the polycondensation followed by the thiol-ene click chemistry. By manipulating the density and length of PEG side chains (Mn = 550, 1000, 2000) to adjust the fine structure of the micro-phase separation, the gas separation performance of the PES-g-PEG membrane was optimized. The PES-g-PEG polymers have two glass transition temperatures (Tg), which are attributed to the PES main chain and PEG side chains. The Tg-PEG and Tg-PES difference (ΔTg) is highly correlated with the PEG side chain density and can be used to interpret the phase separation degree. The copolymer membrane with shorter PEG side chains achieved higher chain density and more developed micro-phase separation, which was facilitated by thermal annealing. As a result, PES A-g-PEG550 membrane shows the best gas separation performance with the CO2 permeability of 26.8 Barrer and the CO2/N2 selectivity of 27.6. The permeability variation with the microstructure of PES-g-PEG mostly relies on the side chain density rather than volume fraction or side chain molecular weight. We believe this study of the gas separation performance of the comb-like copolymer material is meaningful for the further application of membrane technology in CO2 capture and separation.